二氢甲基甲硅烷基阳离子 | 27516-00-3

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 中文名称: 二氢甲基甲硅烷基阳离子
• 英文名称: Methylsilyl-Kation
• 英文别名: Methylsilanylium
• CAS: 27516-00-3
• 化学式: CH₅Si
• 分子量: 45.1362
• InChiKey: MPYTXQCNKGOPPI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.33
• 重原子数：
  2
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  环戊烷 、 二氢甲基甲硅烷基阳离子 生成 甲基硅烷 、 Cyclopentylkation
  参考文献：
  名称：

  Precise determination of stabilities of primary, secondary, and tertiary silicenium ions from kinetics and equilibria of hydride-transfer reactions in the gas phase. A quantitative comparison of the stabilities of silicenium and carbonium ions in the gas phase

  摘要：

  DOI：

  10.1021/ja00185a017
• 作为产物：
  描述：

  甲基硅烷 在 硅烷 作用下， 以 gas 为溶剂， 生成 methylsilanyliumdiyl 、 二氢甲基甲硅烷基阳离子
  参考文献：
  名称：

  The reactions of Si⁺ ions with CH₃SiH₃, CH₃SiD₃, C₂H₆, and CH₃CHD₂

  摘要：

  The reactions of Si+ with CH3SiH3, CH3SiD3, C2H6, and CH3CHD2 have been studied in a tandem mass spectrometric apparatus over the kinetic energy range of 1–10 eV laboratory-frame-of reference (LAB). In all systems, the major process is the formation of SiCH+3, as well as SiCH2D+ and SiCHD+2 in the case of the reaction with CH3CHD2. It is shown that in the reaction of Si+ with CH3SiH3 and CH3SiD3, the process is best described as a Walden inversion, while in the reaction with C2H6 and CH3CHD2, the process appears to approximate the spectator stripping model or modified spectator stripping (polarization-reflection model). In the reaction with CH3CHD2, the slight preference of Si+ to strip the CH3 radical rather than the CHD2 radical is shown to be in accord with a cross-sectional energy dependence of approximately E−1.

  DOI：

  10.1063/1.461978

文献信息

• Ion chemistry in tetramethylsilane (CH3)4Si
  作者：S. McGinnis、K. Riehl、P.D. Haaland

  DOI：10.1016/0009-2614(94)01313-k

  日期：1995.1

  The cross sections for simple and dissociative ionization of tetramethylsilane ((CH3)4Si or TMS) by electron impact have been measured using Fourier-transform mass spectrometry. The total ionization cross section is 8.5 x 10−16 cm2 between 30 and 70 eV. The molecular ion is Jahn-Teller unstable, with dissociative ionization to form (CH3)3Si+ dominating the mass spectrum. CH3SiH2+ and CH3Si+ react rapidly

  已经通过傅里叶变换质谱法测量了四甲基硅烷（（CH 3）4 Si或TMS）通过电子撞击进行简单和解离电离的横截面。总电离横截面在30至70 eV之间为8.5 x 10 -16 cm 2。该分子离子是Jahn-Teller不稳定的，具有离解电离形成（CH 3）3 Si +占主导地位的质谱。CH 3 SiH 2 +和CH 3 Si +与TMS快速反应生成（CH 3）3 Si +。（CH3）3 Si +不与TMS反应，但会被背景水蒸气缓慢水合。
• Unimolecular dissociation of methylsilylium and monochloromethylsilylium in the gas phase
  作者：R. Bakhtiar、C. M. Holznagel、D. B. Jacobson

  DOI：10.1021/j100151a014

  日期：1993.12

  The mechanisms for the lowest energy barrier pathways for unimolecular dissociation of CH3SiH2+ and CH3-Si(Cl)H+ were examined in the gas phase by using Fourier transform mass spectrometry (FIMS). Collision-activated dissociation (CAD) by using sustained ''off-resonance'' irradiation (SORI) was used to determine the lowest energy pathways for dissociation. The lowest energy pathway for decomposition of CH3SiH2+ is dehydrogenation. The mechanism for this dehydrogenation process was investigated by studying the decomposition of CH3SiD2+. Unfortunately, isotopic scrambling by reversible 1,2-hydrogen migrations precede dehydrogenation. Hence, no mechanistic information is obtained from this isotopic labeling experiment. SORI-CAD of CH3SiD2+ yields dehydrogenation as H-2 (0.67) and HD (0.33) with no D2 loss. The lowest energy pathway for dissociation of CH3Si(Cl)H+ is elimination of HCl. In contrast to CH3SiD2+, CH3Si(CI)D+ does not undergo isotopic scrambling upon CAD. SORI-CAD of CH3Si(Cl)D+ yields exclusive elimination of HCl(1,2-elimination) to yield CH2SiD+. Hence, the lowest energy pathway for dissociation of CH3Si(Cl)H+ is 1,2-elimination of HCI. 1,1-Elimination of DCl from CH3Si(CI)D+ to yield CH3Si+ is 38 kcal/mol more favorable than the 1,2-elimination process. Consequently, there must be a prohibitive barrier for the energetically more favorable 1,1-elimination process.